JPS60100572A - Nicotine derivative and agent for improving taste and flavor of tobacco composed of said compound - Google Patents

Abstract

NEW MATERIAL:The nicotine derivative of formula. USE:Useful as an agent for improving the taste and flavor of tobacco. It is diluted with ethyl alcohol to a proper concentration, and added to the cut tobacco for the raw material of tobacco product prior to rolling or packaging, in an amount of about 0.001-0.01%(W/V), preferably 0.0005-0.001%(W/W) based on the cut tobacco. Effective to impart the cut tobacco with mildness and the tobacco- like taste and flavor and to give fine smoke of tobacco. It is also useful for improving the taste and flavor of tobacco by adding to the subsidiary material of cigarette such as cigarette paper, filter of a filter-tipped cigarette, etc. in an amount of 0.0001-0.01%(W/W). PREPARATION:The compound of formula can be produced e.g. by dissolving nicotine in acetonitrile, reacting with benzyl bromide, removing the solvent from the reaction mixture, dissolving the residue in dichloromethane, reacting with m-chloroperbenzoic acid, adding water to the reaction mixture, separating the water layer, washing the layer with dichloromethane, and removing water from the product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel nicotine derivative and a tobacco flavor improver comprising the compound. In recent years, cigarette preferences have been rapidly shifting to so-called light-smoking cigarettes with low nicotine and low tar, and at the same time, demands for 6-smoking tastes are becoming increasingly diverse. Therefore, in order to deal with this trend, research is being conducted on various additives including flavoring agents, particularly new aroma agents that are effective in varying the ratio of tobacco flavor and taste.
・The development of 1 has become an important issue.

From this point of view, the present invention has been made for the purpose of providing a new compound that is effective in improving the aroma and taste of tobacco. The present inventors discovered a new compound while conducting research on various nicotine-related compounds, and found that this new compound has a remarkable effect on improving the flavor and aroma of cigarettes, leading to the present invention. . That is, the present invention is a nicotine derivative represented by the following formula and a tobacco flavor improver comprising the compound.

The compound of the above structural formula is N-penzylnicotinium bromide-N'-oxide (hereinafter referred to as "the present compound"). This compound is a brown oil. Furthermore, all of these compounds are new substances that have not been described in any literature.

Table 1 shows the spectral data of this compound.

t()1 IR(crn-');2950,1620,920'I
-1-NMR (δ; ppm): () lance form);
2.30-2.88 (4H, m), 3.20 (311,
s), 3.80~4.04 (21(, m), 4.98~
5.22 (IH, m).

6.04(2I(,s), 7.40-7.70(511
, m).

8.32 (LH, dd), 8.94 (IH, d), 9.
14 (LH, d), 9.40 (1) (, s): (cis form); 2.30-2°86 (4115 m), 288 (3■
], 5) 380-404 (211, m), 4.98-5
．． 22 (11-1, m), 6.04 (211, s),
7.40-7.70 (5I-1, m), 8.32 (],
H, dd).

8, 94 (I II, d), 9.14 (
1) 1, d), 9.40 (II-1, s
) +3C-NMR (δ; ppm): (trans form);
22.17 (CH2), 30.60 (CI-12
), 55.75(CH3), 66, gB(CI
O2), 72.60 (C112), 78.16 (C
1l).

129.99('C1(), 131.45(CH), 1
32.00 (C1l), 134.61 (CII), 1
35.72(C).

147.13 (C1l), 148.24 (C), 150
．． 70 (CI(), 15333 (CI-1): (cis form); 23.81 (cl-i2).

3288 (C112), 41.07 (CI-13)
, 5862 (C112), 6 (i, 87 (C1 (2)
, 70.03(C)I) , 127.07(CH), 1
31.57 (CI-1), 131.57 (CH), 13
4.38 (CI), 136.49 (C), 146.90
(CI().

147.49 (C), 148.19 (CH), 153.
16(CH) Next, an example of the method for synthesizing the nicotine derivative of the present invention will be shown.

Synthesis example of this compound (1) Nicotine 0.817 (5.0 mmol) was added to lQmi
Insoluble in acetonitrile. There benzyl bromide 0
．． Add 7 s/il (s, 0 mm) dropwise and reflux for 1 hour.

After the reaction, the solvent is removed under reduced pressure, and 10 ml of water is added to dissolve. Severe water flow, knee ξ water (35% aqueous solution) 4m
Add 1 lIi'i' and mix with a whisk.

After the reaction, 0.17% of Pd-alumina was added to decompose the unreacted peracid and arsenic, and the mixture was stirred for 7 minutes.
'(1-"i" Filter the lumina and remove the sewage to form a brown oil!
)-/L/ (3;'Gl' 2) ノiMai
'Ij'J is produced by reverse layer chromatography using t't lt<development fR medium.

The concentration of this compound is 1.0! 'i f (3.0 mm) 1) and nicotine as the raw material), the yield was 60%.

The obtained compound has the cis form represented by formula [1] and the formula [
It is a mixture of l-lance isomers represented by [2]], and the ratio of IU obtained by this synthesis method was trans:cis-2:1.

[I] [■] Synthesis example of this compound (IF) 0.81 r (5.0 mmol) of nicotine was added to lQm
Dissolve in 1 liter of acetonitrile. 0.781 (5.0 mmol+) of benzyl bromide was added dropwise thereto, and the mixture was refluxed for 1 hour.

After the reaction, the solvent was removed under reduced pressure and 10ml of dichloromethane was added.
Add and dissolve. Add to this 1.0 metachloroperbenzoic vinegar.
Add 4F (6 mmol) Y and stir at room temperature for 1 hour.

After the reaction, 10 ml of water was added and shaken, water A'JY was removed, and then the aqueous layer was washed 73 times with 10 ml of dichloromethane. The water is then removed under reduced pressure to yield a brown oil. This is purified by reverse layer chromatography using a water-methanol (3:2) mixture as a developing solvent. The yield 11 of this compound 1 is 0.879 (2.5 mm 11101), which is the yield for nicotine with <X4'1.
- The stain was 50%.

The ratio of trans isomer and cis isomer produced by this synthesis method was 3:8.

Synthesis example of this compound (Ill) Nicotine 0.81 f/ (5.0 mm 01) is 10
m1 of acetonitrile 0.78F (5.0 mmol I) 'a:'
ii-t,' i, +I+ fil 'Nsj.

Let it flow.

After the reaction, add 11 ml of solvent and 10 ml of water.
Add and dissolve. Add to this peracid sansui 2 (, water (: 35%)
aqueous solution) 4 ml, potassium molybdate 1.2 g
(5 mi'Jmol) and 1 u. Gives 7 sympathy +1.

After the reaction, 1゛(I-
Add 0.17 g of alumina and stir for 111,1 J. Next, Pd-alumina and precipitate were filtered, and ion exchange (
1) OWEX IW 4) After chromatography, the reduced sewage is removed to obtain a brown oily substance. This is purified by reverse layer chromatography using a water-methanol (3:2) mixture as a developing solvent. The yield of this compound is 0
．． 701 (20 mmol), and the yield was 40% based on the nicotine used as the raw material.

The ratio of trans isomer to cis isomer obtained by this synthetic method was 14
:1.

The above compound of the present invention can be diluted with ethyl alcohol to an appropriate concentration and used as a tobacco flavoring agent.

In this case, the above compound may be used alone, and other tobacco flavorings,
Additives and the like can be appropriately mixed and used. The compound of the present invention is 0.0001 to 001% (about A degree,
Desirably 0.0005 to 0.001% (w
By adding /A, it has the effect of imparting a tobacco-like odor and taste to the shredded tobacco, and imparting fine texture and fullness to the smoke. Types of tobacco whose aroma and taste can be improved by the compounds of the present invention include not only naturally grown leaf tobacco but also scrap tobacco A4.
Regenerated tobacco produced as A.'1, a culture obtained by tissue culture of plants, or natural cellulose A. 9
It is also effective against synthetic tobacco made from tobacco, and is also effective against Baira tobacco and Tosashi/Kobako.

The compounds of the present invention can also be used in cigarette paper for i11, filter πj products for the production of filtered cigarettes, and filter cigarettes for the production of cigarettes. 1, final sniff 111! Monochu 1
tC (approximately 1.0 0 0 1~001% (WA~・), preferably 0.0 0 0 5~0,001%\
7) v) Attachment 7.11, L. It's always a cigarette incense! The floor can be improved and covered.

Example 1 A 10%-L tanol solution of the present compound (trans:cis-2:1) obtained by T'J in the above synthesis example was added to 100 g of the chopped product of the Kawabehi group under the trade name "Mild Seven". On the other hand, as this compound, IJIL. The odor, taste and irritation were compared using a two-point screening test method using an unscented product as a control. The evaluations of 20 specially trained expert panels are shown in Table 2.

Table 2 Classification Odor Taste Stimulation; Ijili flavored product 6 2 5 (Control product) Compound flavored product 14 18 15* (Trans:cis-2:1) (Note) Numbers in the table were evaluated as good. Number of people *marked is 5% Q
No significant difference was shown in the k rate.

Example 2 This compound (trans:cis-3:
The 10% ethanol solution of 8) was added by spraying so that the amount of this compound was 0,001% (Wro) based on the chopped weight, and rolled up, and two points were identified for odor, taste, and irritation as a control for unprocessed products. Comparisons were made using test methods.

The evaluations of 20 specially trained expert panels are shown in Table 3.

Table 3: Unscented product 5 2 7 (Control 111i'J) Product added with this compound 15 18 13 (Trans:cis=3:8) *marked is 5%
This shows that there is a significant difference in the risk rate.

Example 3゜Product name: ``Cabin 85'' engraved 100 pieces of leaves? This compound obtained in the above synthesis example (trans:cis=14:
The 10% ethanol solution of 1) was sprayed to make the amount of this compound 0.001% (w/w) based on the amount of side mold, and rolled up.2. Comparisons were made using a point discrimination test.

The evaluations of 20 expert panels trained in 1.7 are shown in Table 4.

Table 4: Number 1 in the table: Number of people who played 1 song (marked with *) There is no significant difference at a 5% risk level2.

Example: Product name: "Ki4. Bin 85" The compound obtained in the above synthesis example (trans: cis = 2
: 1) A 10% ethanol solution of side-type ill was sprayed with this compound at a concentration of 0.002% (■/W) and rolled up. The aroma and taste were compared using a two-point discrimination test method.The 3'121i11i obtained by 100 regular smokers of "Cabin 85" was at the limit of J for the fifth person.〇Table 5,・H<+H addition 1M ♀ item 2 (age size jId item) (Note) In A, ;1M character IJ: Yoito:, ・P::ii
1. The person with the attack seal has a 13% risk of death.”:
11. It's a shame that there is such a thing.

Example 5 Waste tobacco was soaked in hot water at 100°C, separated into a water-soluble part and a water-insoluble part, and the water-insoluble part was beaten and its dry weight was determined. A mixture containing 15% of Ai's coniferous kraft pulp was molded into thin paper, and this compound was synthesized using the method described above for 50 grams of sheet-shaped recycled tobacco made by adding back the water-soluble portion to the thin paper. (Trans:cis=3:
8) 10% ethanol solution was sprayed and rolled up so that the amount of this compound was 0001% (W/W) based on the amount of side mold, and the unscented product was compared with 2 points 1 for odor, taste and irritation. Comparisons were made using the discrimination test method. The evaluations of 20 expert panels trained in 9゛S are shown in Table 6.

Table 6 Category Odor Taste Stimulating non-flavored product 6 4 4 (Control product) Product added with this compound 14” 16 16 (Note) The numbers in the table indicate the number of people who rated it as good. indicates that there is a significant difference.

Claims (1)

[Claims] 1 general formula Nicotine represented by 1:,5 conductor. 2--Kojitake A tobacco flavor improver comprising a compound represented by: